CHEMICAL PHYSICS LETTERS
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2024
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IF 2.8
Ting-ting Yan,Yi-fei Xu,Dong-yang Xi,Zhiqing Yu,Long Ma,Dan-dan Zhang,Ran Jiang
The study investigated the behavior of N-nitropyrazole (1-NP, C 3 H 3 N 3 O 2 ) under high pressure using a diamond anvil cell, Raman spectroscopy, and simulation calculations. The pressure–volume relationship of the sample, molecular interactions, and changes in optical Raman were analyzed. The Raman experiments revealed abnormal vibration intensities and a discontinuity in peak position at 2.2 GPa. For instance, the C-H stretching vibration produces a new vibration peak under pressure, and the NO 2 torsion mode continues to red shift beyond 2.2 GPa. These observations suggest that the crystal’s phase transition results from the distortion of its hydrogen-bonded network structure. The pressure relief experiment confirms the reversibility of the phase transition.
研究领域:
化学
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材料科学
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PHYSICS LETTERS A
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2024
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IF 2.3
Ting-ting Yan,Yi-fei Xu,Dong-yang Xi,Zhi-qing Yu,Ran Jiang,Dan-dan Zhang
The study investigates the structural stability of the hydrogen-bonded energetic material 4-nitropyrazole (4-NP, C 3 H 3 N 3 O 2 ) from ambient pressure to 10 GPa at room temperature using diamond anvil cell (DAC) and Raman spectroscopy. Based on the changes observed in the high-pressure Raman spectra, it is proposed that the hydrogen-bonded energetic material 4-NP undergoes a phase transition within the pressure range of 2.7–6.4 GPa. Upon complete pressure release from 10 GPa, the resulting spectrum is consistent with the Raman spectrum observed under ambient pressure, indicating that the phase transition is reversible. Ab initio calculations were used to explain the changes in molecular arrangements and hydrogen-bonded networks. Hirshfeld surfaces and fingerprint plots were used to directly compare the variations in packing patterns and intermolecular interactions. Based on the experimental and calculated results, it is proposed that the phase transition of 4-NP was likely caused by the rearrangements of the hydrogen-bonded networks.
研究领域:
材料科学
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化学
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JOURNAL OF SOLUTION CHEMISTRY
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2025
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IF 1.3
Wang Mingya,Pan Hongxia,Liu Yongzheng,Shi Junli,Shen Fanfan,Cao Duanlin,Zhao Linxiu
1,3-Dinitropyrazole serves as a crucial intermediate in pharmaceutical synthesis and is also recognized as a high-energy density material. Its purity can affect the yield, safety, and stability of the product. Recrystallization is a pivotal step in its purification. This study investigates the solubility of 1,3-dinitropyrazole in twelve solvents, offering guidance for the selection of appropriate solvents. The solubility of 1,3-dinitropyrazole in a selection of twelve solvents, including water, methanol, ethanol, acetonitrile, hexane, cyclohexane, dichloromethane, dichloroethane, benzene, toluene, ethyl acetate, and acetone, was measured by the gravimetric technique across a temperature spectrum from 278.15 to 318.15 K at atmospheric pressure. Under ambient conditions at 298.15 K, the order of solubility was as follows: acetonitrile (48.201 × 10 –2 ) > acetone (45.012 × 10 –2 ) > dichloromethane (37.019 × 10 –2 ) > ethyl acetate (36.088 × 10 –2 ) > dichloroethane (33.244 × 10 –2 ) > benzene (19.563 × 10 –2 ) > methylbenzene (15.221 × 10 –2 ) > methanol (5.531 × 10 –2 ) > ethyl alcohol (3.078 × 10 –2 ) > cyclohexane (0.060 × 10 –2 ) > hexane (0.053 × 10 –2 ) > water (0.051 × 10 –2 ). Additionally, the solubility in these 12 pure solvents increases as the temperature rises. The efficacy of four established thermodynamic models, including the Apelblat equation, Jouyban–Acree model, van’t Hoff model, and λ h model, was evaluated via R 2 , ARD and RMSD criteria. Notably, the Apelblat equation and Jouyban–Acree models demonstrated exceptional accuracy, with the Jouyban–Acree model emerging as the optimal choice for predicting the solubility of 1,3-dinitropyrazole. Meanwhile, the application of Hansen solubility parameters in predicting and analyzing solubility also has its limitations. The data pertaining to the solid–liquid equilibrium of 1,3-dinitropyrazole across a range of solvents are indispensable for the initial assessment of its utility in industrial contexts.
研究领域:
化学工程
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材料科学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2025
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IF 2.1
Mingya Wang,Hongxia Pan,Yongzheng Liu,Jun Chen,Duanlin Cao,Linxiu Zhao
3(5)-Nitropyrazole is obtained by rearrangement of 1-nitropyrazole in high boiling organic solvents. In this paper, the solubility of 3(5)-nitropyrazole in 12 high boiling solvents (anisole, benzonitrile, mesitylene, o-dichlorobenzene, 1-octanol, benzyl alcohol, 2-ethylhexyl acetate, dimethyl glutarate, cyclohexanone, N,N-dimethylformamide, N-methylformamide, and isophorone) was determined using the static gravimetric method over the temperature range of 283.15–323.15 K. The experimental results revealed that the solubility of 3(5)-nitropyrazole exhibited a positive correlation with temperature. Under ambient conditions at 298.15 K, the solubility decreased in the following order: N,N-dimethylformamide (37.705 × 10–2), N-methylformamide (20.131 × 10–2), cyclohexanone (13.469 × 10–2), isophorone (11.957 × 10–2), dimethyl glutarate (6.667 × 10–2), benzyl alcohol (3.909 × 10–2), benzonitrile (2.915 × 10–2), 1-octanol (1.916 × 10–2), 2-ethylhexyl acetate (1.220 × 10–2), o-dichlorobenzene (0.666 × 10–2), anisole (0.688 × 10–2), and mesitylene (0.246 × 10–2). The solubility of 3(5)-nitropyrazole was fitted using the Apelblat equation, λh equation, NRTL model, and van’t Hoff model. The fitting results were evaluated using average relative deviation and RMSD. The NRTL model exhibited the best overall performance. The use of Hansen solubility parameters for solubility prediction and analysis has certain limitations.
研究领域:
化学工程
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物理化学
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高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2023
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IF 2.6
Fanfan Shen,Xinqiang Pang,Yongzheng Liu,Linxiu Zhao,Fang Chen,Yongxiang Li,Duanlin Cao
The solubility and thermodynamic properties of N-nitropyrazole (N-NP) in different pure solvents are crucial for crystallization, purification, and further theoretical research. The solid–liquid equilibrium solubility of N-NP in the range of 293.15–323.15 K was determined in 12 pure solvents of water, mesitylene, n-hexane, cyclohexane, ethanol, chlorobenzene, benzonitrile, propylene glycol, anisole, dimethyl sulfoxide, N,N-dimethylformamide, and o-dichlorobenzene by the laser dynamic method at an atmospheric pressure of 0.1 MPa. In the temperature range of 293.15–323.15 K, the solubility of N-NP in water, mesitylene, n-hexane, cyclohexane, ethanol, chlorobenzene, benzonitrile, propylene glycol, anisole, dimethyl sulfoxide, N,N-dimethylformamide, and o-dichlorobenzene displayed the mole fraction solubility of 0.001271–0.003540, 0.033858–0.139782, 0.001966–0.009268, 0.002621–0.013898, 0.013601–0.058669, 0.097849–0.310726, 0.170722–0.387823, 0.017647–0.065427, 0.069507–0.379656, 0.225911–0.457260, 0.210072–0.415353, and 0.017651–0.172345, respectively. The measured solubility data of N-NP had a good correlation with the modified Apelblat equation, the NRTL equation, the Wilson equation, as well as the λh equation. Through the comparison of the minor average of the root-mean-square deviation (103RMSD) and the coefficient of determination (R2), the Wilson equation yielded a more satisfactory correlation result. Thermodynamic parameters of mixing enthalpy (ΔmixH), mixing entropy (ΔmixS), and mixing Gibbs energy (ΔmixG) were calculated and analyzed based on the experimental data. The positive ΔmixH and ΔmixS implied that the dissolution process of N-NP in the selected solvents was endothermic and entropy-driven. The relative contributions of enthalpy and entropy demonstrated that enthalpy was the main contributor to the Gibbs free energy in the dissolution process. In addition, the solute–solvent interaction was calculated to elaborate the solubility of N-NP in selected solvents deeply. In addition, the solid–liquid surface tension and the surface entropy factor of N-NP were discussed on the basis of the experimental solubility data.
研究领域:
化学工程
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物理化学
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CRYSTAL GROWTH & DESIGN
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2022
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IF 4.01
Qamar-un-Nisa Tariq,Yu-fan Bi,Saira Manzoor,Maher-un-Nisa Tariq,Wen-Li Cao,Wen-Shuai Dong,Jian-Guo Zhang
Due to the acidity and the limited applications of 3,4-dinitropyrazole (DNP), two types of nitrogen-rich energetic cocrystals (DD1 and DD2) based on DNP and 3,4-diaminofurazan (DAF) were synthesized. The magnificently grown cocrystals were thoroughly examined by Fourier transform infrared spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, elemental analysis, and nuclear magnetic resonance. A differential scanning calorimetry analysis revealed that both cocrystals have different endothermic peaks and remarkably similar exothermic peaks. Moreover, thermogravimetric analysis demonstrates that the thermal decomposition of DD1 and DD2 seems to be three mass loss stages. Hirshfeld surface analysis suggests that O···H (hydrogen bonding) close contacts contribute the most to the stabilization of DD1 and DD2. Subsequently, the pH values of DD1 and DD2 indicate that cocrystals reduce the acidity of DNP; additionally, the inclusion of hydrogen peroxide can improve the oxygen balance of the cocrystal to a certain degree. The obtained cocrystals have high nitrogen contents and acceptable sensitivities to external stimuli (friction and impact) that prove them as promising candidates for expanding the applications of DNP in the field of energetic materials after overcoming an acidity problem.
研究领域:
化学
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材料科学
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Energetic Materials Frontiers
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2025
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IF 3.9
Yang-rui Cui,Jian-shuo Cheng,Yuan-gang Xu,Ming Lu
Pyrazole derivatives with polynitro groups were extensively researched in energetic material field as they show high energy density and excellent detonation properties, but the specific synthesis process still encounters challenges. In this paper, we firstly combined trinitromethyl, dinitroethyl, oxadiazolyl moieties with pyrazole, successfully designed and synthesized three novel poly-nitro pyrazole energetic compounds by nitration. Their structural features were investigated using single-crystal X-ray diffraction, nuclear magnetic resonance, infrared spectroscopy. 3-(3,5-Dinitro-1 H -pyrazol-4-yl)-1,2,4-oxadiazol-5(4 H )-one ( 12 ) possessed a superior thermal stability (235.1 °C) due to the presence of strong conjugated interaction in this structure. Among all, 3-nitro-1-(trinitromethyl)-1 H -pyrazole-5-carboxylic acid ( 8 ) exhibited a good thermal stability (163.7 °C), a high density of 1.829 g cm −3 at 298 K in combination with excellent detonation properties ( D : 8747 m s −1 ; P : 33.613 GPa). The results indicate that three compounds have promise to act as novel energetic materials and the synthesis provides a direction for polynitro compounds and oxadiazol based energetic compounds.
研究领域:
有机化学
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含能材料化学
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物理化学
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结构化学
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热力学
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爆炸力学
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分子设计
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高影响因子
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